The Jambos bowed out at the second round stage last year so will expect to progress further this time around, while their hosts are outsiders to make it through the competition's first phase.
Match preview
Building up to their Premiership opener, at home to Celtic at the end of July, first Hearts must visit Balmoor to get their cup campaign underway.
Finding themselves in a section containing ambitious Cove Rangers, Stirling Albion, Inverness Caley Thistle and this weekend's opponents Peterhead, Robbie Neilson's men will be strong favourites to come out on top.
In the last leg of their pre-season, Neilson saw his side beat League One side Falkirk 4-0 last weekend, before cruising to a 3-0 win at minnows Bonnyrigg Rose Athletic in midweek.
A youthful Hearts side overcame Bonnyrigg at rain-soaked New Dundas Park on Thursday, as French striker Armand Gnanduillet netted either side of the half-time interval.
In all, the Edinburgh side went unbeaten in five warm-up friendlies against lower-league and non-league opponents, so should travel north in high spirits this weekend.
Opponents Peterhead, meanwhile, may consider that playing a Premiership side in their opening League Cup game is an unkind quirk of the fixture computer: the Blue Toon are ranked well below Hearts in the Scottish league pyramid and certainly start as underdogs.
While the newly-promoted Jambos are the Group A favourites - the first of two higher-ranked teams in Peterhead's first two games - such a stern test to open may ultimately prove beneficial, with more straightforward fixtures to come.
They will not write off their chances of an upset though, and striker Russell McLean is not a stranger to creating a League Cup upset: in his first spell at the Aberdeenshire club, he was in the team which shocked Hearts 2-1 at Balmoor back in 2017.
In the build-up to the 2020-21 campaign, Jim McInally's men have played a handful of pre-season friendlies - despite their match against Turriff United being called off due to a positive COVID-19 case - beating Inverurie Locos 2-1, drawing 1-1 with Forfar and winning 4-3 against Broughty Athletic.
Former Montrose forward McLean bagged the equaliser versus Forfar and will be a key component of the XI that attempt to make a successful return to competitive action this week.
Peterhead form (all competitions):
Hearts form (all competitions):
Team News
Hearts manager Robbie Neilson fielded an inexperienced team in friendly games during the last week, including young Finlay Pollock, who continues to establish himself as a contender for first-choice status.
In midweek, Jamie Walker, Euan Henderson and Armand Gnanduillet were all included too - as well as former Hull City defender Stephen Kingsley - so all four are in pole position to make the XI again this weekend.
Both Kingsley and Jordan Roberts have spent time out injured, so benefited from some on-field minutes, and are now fit to start.
Winger Josh Ginnelly and goalkeeper Ross Stewart recently signed permanent deals after spending last season on loan at Tynecastle, while Brighton defender Alex Cochrane arrived last week on a season-long loan - all three should feature at some stage on Saturday.
Peterhead wrapped up preparations for their League Cup campaign with a win over Broughty Athletic, which saw a number of players pick up knocks that could potentially rule them out of the opener against Hearts.
Meanwhile, forward Paul Sludden scored at both ends of the game, with Jordon Brown also netting, and the pair should be available to start at Balmoor.
Peterhead possible starting lineup:
Rae; J. Brown, Bailey, Freeman; S. Brown, Ferry, Kesson, Mulligan, Fraser; Sludden, Boyd
Hearts possible starting lineup:
Stewart; C. Smith, Flatman, Souttar, Kingsley, Watson; Pollock, Walker, Roberts, Henderson; Gnanduillet
We say: Peterhead 0-2 Hearts
Undoubtedly, few would expect Peterhead to repeat their heroics of 2017 this weekend, as Hearts have an SPL campaign to warm up for and should already be sharp enough to confirm their superiority.
The Jambos may not field a full-strength side just yet, but have sufficient firepower to see off the hosts' challenge.